Process for polymerization of alkylene oxides with metal salts



FOR POLYMERIZATION or ALKYLENE PROCESS OXIDES WITH METAL SALTS Arthur E. Gurgiolo,'Lake Jackson, Tex., assi'gnor to The No Drawing. Application July 22, 1958 Serial No. 150,019

13 Claims. (Cl. 260-2) This inventionirelates to a process for the polymerization of a lower alkylene oxide to a polymeric material under the catalytic; influence of certain organic acid salts.

Moreparticularly, the process pertains to polymerization of olefin oxides, particularly ethylene oxide and propylene oxide, by employing salts of fatty acids and aliphatic diand tricarboxylic acids having from 1 to 30 carbon atoms and aromatic monoand dicarboxylic acids having up to 3 aromatic rings of group II metals having an atomic number in the range of 12 to 57 and trivalent metals of ferric iron and aluminum. The group II metals are magnesium, calcium, zinc, strontium, cadmium, and barium. Of the above metals, salts of calcium, barium, and strontium are particularly eflective as catalysts.

Illustrative examples of the organic acids which form the metal salt effective in catalyzing the polymerization of lower alkylene oxides are formic, acetic, propionic, butyric, valeric, caproic, caprylic, capric, lauric, myristic, palmitic, stearic, behenic, cerotic and naphthenic of the. saturated fatty acids; acrylic, methacrylic, crotonic and sorbic of the unsaturated fatty acids; oxalic, malonic, succinic, pimelic, sebacic, ma'leic', citric, and tricarballylic of the aliphatic diand tricarboxylic acids; and benzoic, naphthoic, authroic, phthalic, and naphthalic of the aromatic monoand dicarboxylic acids.

The amount of catalyst that is employed is ordinarily between from 0.1 to 6 percent by weight, based on the weight of the alkylene oxide monomer being polymerized. Preferably an amount of the catalyst in the neighborhood of 0.5 to 2 percent by weight is utilized. The employment of the preferred amount of catalyst for accomplishing the polymerizationordinarily secures optimum rates of reaction or complete conversion of the monomer to a high molecular weight polymer.

Solid ethylene oxide polymers=may be obtained by practice of the invention which are white crystalline solids and have at least one and usually more of a variety of United S ates P wn, r

2,934,505 Patented Apr. 26, 1960- ice.

may be used in coating application, as thickeners, sizingagents, binders, and as components in polyurethene foam, or as a reactive constituent in other plastic materials.

In the polymerization of the alkylene oxide, the monomer and-the catalyst may be simply mixed together and charged into a closed vessel and heated until the polymerization is complete. It is usually beneficial for the reaction mass to be agitated during the polymerization. Temperatures in the range of about to 150 C. may be used. At the lower temperatures, higher yield of the high molecular weight or solid polymer may be realized, but the polymerization time is generally longer and may extend to 200 hours or more. At the high temperatures, the rate of reaction is relatively rapid and a suitable point for the termination of the reaction may be reached in less than 3 hours. However, at these high temperatures, the yield of the solid resin obtained may decrease. In order to obtain a fairly rapid rate of reaction with a suitable yield of the desired solid polymer, the polymerization is ordinarily carried out at a'temperature between 80 and 130 C., the optimum temperature being about 100 C. At the temperatures of 80- to 130 C.,' the polymerization usually is substantially com, pleted in about 18 to 120 hours, the optimum being from 24 to 60 hours.

The polymerization rate may be increased by carrying out the reaction in the presence of a trace amount of water. With a trace of water, the polymerization of the alkylene oxide may be effected in /2 to 3 hours which without the water may require 24 hours or'more. Sincethe presence of water in relatively large amounts? has a tendency to lower the molecular weight of the: polymer obtained, only a trace amount of water is used; Generally the amount of water employed is .not greater: than 0.2 weight percent of the catalyst with 0.1 to 0.125:

weight percent of the catalyst being preferred.

The polymerizationmay also be carried out in a suit; able inert non-aqueous diluent medium. The employ-- ment of such a medium for the polymerization mayuses including the preparation of moldings, films, fibers and in coating applications. They generally provide high tensile strength fabricated articles that are possessed of good dielectric characteristics. They may also be used as thickeners, sizing agents, and binders. The solid polymers are soluble in water, acetonitrile, chloroform, formaldehyde, and methanol and insoluble in methyl ethyl ketone, ethyl acetate, and carbon tetrachloride. The reduced viscosities of these polymers, measured in acetonitrile at a concentration of 0.2 gram per 100 ml. of solvent at a temperature of 30 'C., are above 0.1.

The reduced viscosity which is an indication of the molecular weight of a polymer is obtained, by dividing the specific viscosity of a solution of the polymer in a solvent by the concentration of the polymer in the solution measured in grams of the polymer per 100 ml. of solvent. The specific viscosity is obtained by dividing the difference in the viscosity of the solution and viscosity of the pure solvent by the viscosity of the solvent. The propylene oxide polymers obtained by the process are high molecular weight liquid or waxy polymers which sometimes tend to reduce the rate of the reaction, although, in certain instances, it may facilitate the achievement of a more nearly complete copolymerization of the monomer; -The medium either may be a solvent or a non-solvent suspending medium. It is advantageous for the diluent 'medium that is employed to'boil at about the desired polymerization temperature. In this way, the utilization of reflux techniques permits an easy means for the regulation of the reaction temperature. Diethyl ether, diisopropyl ether, petroleum ether, benzene, nhexane and the like provide beneficial solvent characteristics for employment in the polymerization. While various low boiling, liquid, non-solvent media may also be emploved, it is usually more desirable to utilize solvents; The inert non-aqueous diluent medium may generally be used in a quantity that is approximately equal to the quantity of the monomers being so polymerized.

The-polymeric product may be recovered and purified from the reaction mass according to several procedures. apparent to those skilled in the art. For example, the unreacted monomer and the solvent or other diluent medium (when one has been employed) may be strippedfrom the reaction mass by vaporization to leave the polymeric material. The crude polymer may bea thick viscous liquid or may be in the form of a tough, rubberlike to a wax-like solid associated with liquid polymers that may have beenformed during the reaction. The solid'polymer may be separated from the reaction product by dissolving the product -in a, suitable solvent, such as hot acetone or acetonitrile, and the solid polymer precipitated or crystallized from the solution by cooling the-solution'at a low temperature, generally about r29?- C. or below. Recrystallization may be employed for diluted to 25 ml. with hexane. The resulting solution further purification until a suitable solid polymeric macontained 1 weight percent calcium and 0.2 weight perterial is obtained. The liquid polymers are then obtained cent water. One milliliter of the resulting solution obby evaporation of the solvent. tained above was used as catalyst for the polymerization By the process of the invention, polymersof other 5 of grams of ethylene oxide. The polymerization was olefin oxides besides ethylene oxide and propylene oxide carried out at 130 C. in a manner similar to that demay also be prepared. Solid polymers of such lower scribed in Example I. olefin oxides as chloropropylene oxide, which is also In a polymerization time of 90 minutes, 14.5 grams known as epichlorohydrin, isobutylene oxide and others of a hard white brittle wax was obtained. The product that contain not more than four carbon atoms in their to had a reduced viscosity, at 0.2 weight percent concenmolecules may also be obtained. tration in acetonitrile at 30 C. of 0.345 which indicated The following examples further illustrate the invention. a molecular weight of 30,000.

Example I In the second run, a 5 grams sample of calcium naphthenate containing 4 weight percent calcium and 0.5

A Series Of runs was ma e Where ethylene Oxide and 15 weight percent water was diluted to give a solution con- Propylene oxide were polymerized with diffefehteata1YStS- taining 1 weight percent calcium and 0.125 weight per- In h r n a gl i l, 1 inch in diameter and 5 cent water. One milliliter of the resulting solution was inches long, was used as the reaetor- The V131 was used as catalyst for the polymerization of 15 grams of purged with nitrogen and then a given amount of eatalyst ethylene oxide in a manner described above. In a polyehd 15 grams of the monomer were d The Vial g0 merization time of 45 minutes, 13.8 grams of a hard, and its contents were chilled in a Dry Ice-acetone bath, tough, white fibrous polymer was obtained. The res al d. an allowed t come to m temperature. duced viscosity of the product under the condition de- After the vial d Come to room temperature: it was scribed above was 1.125 which indicated a molecular placed in a rotating steam heated autoclave which was i h f 100,00()

maintained at 130 C. where the monomer in the vial h i l i d i was allowed to pe y h for Predeieflninfl1 time- 1. A process for the polymerization of a lower alkylene After the polym rlz the Vlal was {emoved from oxide containing not more than 4 carbon atoms in its the autoclave, opened, and the unpolymenzed monomer molecule to a polymeric material, which comprises vaporized. The polymer obtained was weighed.

Solid polymers of ethylene oxide were obtained, while the propylene oxide polymers were thick viscous slightly cloudy syrups or waxes. The ethylene oxide polymers were white in color and were molded into water soluble ing the alkylene oxide with from 0.1 to 6 weight percent of a catalyst selected from the group consisting of salts of unsubstituted fatty acids having from 1 to 30 carbon atoms and unsubstituted aliphatic diand tricarboxylic acids films which could be oriented by Stretching The having up to 30 carbon atoms and unsubstituted aromatic duced viscosities of some of the solid polymers were dem g i 4 havmg P to 1 3 23: termined on the basis of acetonitrile solutions containrmgs 0 rouP meta S avmg an aonPc e 1 ing 0.2 gram of polymer per 100 ml. of acetonitrile at range of 12 to heating the resultmg l a 30 C temperature of from 30 to 150 C. for a perlod of tune The results obtained and other pertinent data are suffieieht Pelymerize the Olefin Wilde, and sepafatlng shown in the table below. the polymeric material from the reaction mass.

Amount Weight Percent Reduced of Reaction of Conver- Viscosity Catalyst Catalyst Monomer Time, Polymer, slon of of Weight, Hours Grams Monomer Polymer Percent Calcium Acetate-H1O ethylene oxide..... 1% 100 15 14.2 15 11.1 .5 15 14.2 14.3 15 15 12.8 2 3.2 14 Zinc Stearate 8.8 Cadmium Stearate-...- 13. 5

Magnesium 0xalate Calc]i)um Acetate.. o

Example II Q 7 2. A process according to claim 1 wherein the olefin 'de is propylene oxide. To illustrate the effect of a trace amount of water OX1 in the polymerization reaction, two runs were made A process according to chum 1 wherem the olefin 'de is ethylene oxide. where ethylene oxide was polymerized using calcium 0X1 7 naphthenate as catalyst with the catalyst containing a Apmcess for the Polymenlatlon of Propylene made l which comprises mixing the different amount of water in each of the runs. 1 to a P Y e In the first run, a 5 grams sample of a solution of pfeljylene QXlde wlth from 6 welghtpefeeht of calcium naphthenate i i l pirits containing 5 barium stearate as catalyst, heating the resulting mixture weight percent calcium and 1 weight percent water was to a temperature of from 30 to C. for a period of time suflicient to polymerize the propylene oxide, and separating the polymeric material from the reaction mass.

5. A process for the polymerization of propylene oxide to a polymeric material, which comprises mixing the propylene oxide with from 0.5 to 2 weight percent of barium stearate, heating the resulting mixture to a temperature of from 80 C. to 130 C. for a time of from 18 to 120 hours, and separating the polymeric material from the reaction mass.

6. A process for the polymerization of propylene oxide to a polymeric material, which comprises mixing the propylene oxide with from 0.1 to 6 weight percent of calcium stearate, heating the resulting mixture to a temperature of from 30 to 150 C. for a period of time sufiicient to polymerize the propylene oxide, and separating the polymeric material from the reaction mass.

7. A process for the polymerization of propylene oxide to a polymeric material, which comprises mixing the propylene oxide with 0.5 to 2 weight percent of calcium stearate, heating the resulting mixture to a temperature of from 80 C. to 130 C. for a time of from 18 to 120 hours, and separating the polymeric material from the reaction mass.

8. A process for the polymerization of ethylene oxide to a solid polymeric material, which comprises mixing the ethylene oxide with from 0.1 to 6 weight percent of barium stearate as catalyst, heating the resulting mixture to a temperature of from 30 to 150 C. for a period of time sufficient to polymerize the ethylene oxide, and separating the solid polymeric material from the reaction mass.

9. A process for the polymerization of ethylene oxide to a solid polymeric material, which comprises mixing the ethylene oxide with 0.5 to 2 weight percent of barium 6 stearate, heating the resulting mixture to a temperature of from 30 C. to 130 C. for a time of from 18 to 120 hours, and separating the solid polymeric material from the reaction mass.

10. A process for the polymerization of ethylene oxide to a solid polymeric material, which comprises mixing the alkylene oxide with from 0.1 to 6 weight percent of ca1- cium stearate as catalyst, heating the resulting mixture to a temperature of from 30 to 150 C. for a period of time suflicient to polymerize the ethylene oxide, and separating the solid polymeric material from the reaction mass.

11. A process for the polymerization of ethylene oxide to a solid polymeric material, which comprises mixing the ethylene oxide with 0.5 to 2 weight percent of calcium stearate, heating the resulting mixture to a temperature of from C. to 130 C. for a time of from 18 to hours, and separating the solid polymeric material from the reaction mass.

12. A process for the polymerization of ethylene oxide to a solid polymeric material, which comprises mixing the ethylene oxide with from 0.1 to 6 weight percent of calcium naphthenate containing not more than 0.2 weight percent of water, heating the resulting mixture to a temperature in the range of 30 C. to 150 C. for from h to 3 hours, and separating the solid polymeric material from the reaction mass.

13. A process according to claim 12, wherein the ethylene oxide is mixed with from 0.5 to 2 weight percent of calcium naphthenate containing from 0.1 to 0.125 weight percent water, and the mixture is heated to a temperature in the range of 80 to C.

No references cited. 

1. A PROCESS FOR THE POLYMERIZATION OF A LOWER ALKYLENE OXIDE CONTAINING NOT MORE THAN 4 CARBON ATOMS IN ITS MOLECULE TO A POLYMERIC MATERIAL, WHICH COMPRISES MIXING THE ALKYLENE OXIDE WITH FROM 0.1 TO 6 WEIGHT PERCENT OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF SALTS OF UNSUBSTITUTED FATTY ACIDS HAVING FROM 1 TO 6 CARBON ATOMS AND UNSUBSTITUTE ALPHATIC DI- AND TRICARBOXYLIC ACIDS HAVING UP TO 30 CARBON ATOMS AND UNSUBSTITUTED AROMATIC MOMO- AND DICARBOXYLIC ACIDS HAVING UP TO 3 AROMATIC RINGS OF GROUP II METALS HAVING AN ATOMIC NUMBER IN THE RANGE OF 12 TO 57, HEATING THE RESULTING MIXTURE TO A TEMPERATURE OF FROM 30* TO 150*C. FOR A PERIOD OF TIME SUFFICIENT TO POLYMERIZE THE OLEFIN OXIDE, AND SEPARATING THE POLYMERIC MATERIAL FROM THE REACTION MASS. 